JP2555513B2 - Method for producing tetrachlorethylene - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing tetrachloroethylene.

[0002]

2. Description of the Related Art Conventionally, tetrachloroethylene has 3 carbon atoms.
Thermal chlorinolysis reaction in which the following hydrocarbons such as methane, ethane, ethylene, propane, propylene, or their partial chlorinated compounds are reacted with chlorine gas at 450-750 ° C.
It is manufactured by chlorinolysis, but carbon tetrachloride is also co-produced at this time. However, carbon tetrachloride destroys the ozone layer, so in the near future, it will
Use is about to be banned. Carbon tetrachloride is not only co-produced with tetrachloroethylene, but is also produced as a by-product during the production of chloroform from methane and the production of trichlorethylene from ethylene chloride.

Therefore, many attempts have been made to convert carbon tetrachloride into tetrachloroethylene. For example, carbon tetrachloride is disproportionated with methane or methylene chloride at high temperature (di
There is an attempt to convert it into tetrachloroethylene by sproportionation), but the selectivity of tetrachloroethylene is low (US Pat. No. 3,726,932, Chem. Abstr. 79-18046k). Pyrolysis of carbon tetrachloride in the presence of nitrogen gas (Chem.Abs
tr.59-178187t), the yield of tetrachlorethylene is only about 50% at the reaction temperature of 650-900 ℃. When chloroform, methylene chloride, hydrogen, methane, etc. are added to the reaction, the yield is increased but the tar-like substances are by-produced. In the method of pyrolyzing carbon tetrachloride in a quartz-filled reaction tube in the presence of chloroform, the yield of tetrachloroethylene is about 77% (Chem.Abstr.83-178187t). The method of thermally decomposing carbon tetrachloride in a carbon-filled tube, preferably at 850 to 930 ° C. (JP-A-50-117704), produces a large amount of hexachlorobenzene as a by-product and has a high reaction temperature, which is not practical.

It is also known that there is an equilibrium reaction between carbon tetrachloride and tetrachloroethylene as shown in the following formula (1) (for example, Journal of Industrial Chemistry 70 (9), 1482-5, ('6
(See 7))

[Formula 1] It is theoretically possible to produce tetrachloroethylene from carbon tetrachloride by utilizing the equilibrium reaction of formula (1), but tetrachloroethylene is produced by an endothermic reaction (ΔH
₂₉₈ = + 185.5kj) and requires a high temperature of about 700 ° C [soda and chlorine 42 (8), 310 (91)] and a large amount of high-boiling substances such as hexachlorobenzene as a by-product, which is a practical industrial method. It is difficult to convert. Furthermore, a method of producing tetrachloroethylene by adding ethylene to the by-product chloride at the time of vinyl chloride production and thermally chlorinating and decomposing it under the condition of 1-10 mol% excess chlorine in the presence of carbon tetrachloride used in circulation (Poland Japanese Patent No. 140824) has also been proposed, but it has a low industrial value due to the large amount of by-products of partially chlorinated hydrocarbons and high boiling points.

[0005]

As described above, while the use of carbon tetrachloride is about to be prohibited, an industrially feasible method for converting coproduced carbon tetrachloride into tetrachloroethylene has been developed. Not not. Therefore, there is a demand for development of a method for producing tetrachloroethylene that does not accompany byproduct of carbon tetrachloride. Therefore, it is an object of the present invention to provide a method for producing tetrachlorethylene that does not co-produce carbon tetrachloride and has less by-products of highly chlorinated high-boiling substances that are difficult to convert to useful substances.

[0006]

The present invention is a method for producing tetrachloroethylene which does not produce carbon tetrachloride as a by-product and has a small amount of highly chlorinated high-boiling substances as by-products. It is a hydrocarbon having 3 or less carbon atoms or 3 carbon atoms. While supplying the following partially chlorinated hydrocarbons or their mixtures with carbon tetrachloride,
To produce tetrachloroethylene by reacting at ~ 700 ℃, the amount of carbon tetrachloride in the produced reaction gas is equal to or less than the amount of supplied carbon tetrachloride, and the chlorine concentration in the reaction produced gas is 7 to 15 mol%. Take out the reaction product gas in the state,
It is characterized in that tetrachloroethylene is separated by distillation and the total amount of carbon tetrachloride and chlorine gas in the reaction product gas are recycled.

The present invention will be described in detail below. As the hydrocarbon having 3 or less carbon atoms used in the present invention, for example, any one of propane, propylene, ethane, ethylene, methane, or a mixture thereof in an arbitrary ratio can be used. Examples of partially chlorinated hydrocarbons having 3 or less carbon atoms include propylene chloride, ethylene chloride, trichloroethylene, trichloroethanes, dichloroethylenes, chloroform, methylene chloride, and ethane as a by-product in the production of vinyl chloride or vinylidene chloride. And a mixture of partially chlorinated compounds such as ethylene. These hydrocarbons having 3 or less carbon atoms and /
Alternatively, while supplying a partially chlorinated hydrocarbon having 3 or less carbon atoms (hereinafter referred to as hydrocarbons) together with carbon tetrachloride, chlorine gas and 500 to 700 ° C, preferably 550 to 650 ° C, more preferably 560 to 630. ℃, pressure in the reactor 100-200kPa
Then, the reaction is performed for 0.1 to 10 seconds, preferably 0.5 to 5 seconds.

When the hydrocarbons are supplied together with carbon tetrachloride and reacted with chlorine gas as in the method of the present invention,
Hydrocarbons produce tetrachloroethylene and carbon tetrachloride by a thermal chlorinolysis reaction, and at the same time, a considerable amount or more of the produced carbon tetrachloride reacts with hydrocarbons to produce tetrachloroethylene.

In a system in which a thermal chlorination decomposition reaction of hydrocarbons is carried out, when carbon tetrachloride is reacted with hydrocarbons or hydrogen or a mixture thereof to convert into tetrachloroethylene, a high-boiling substance such as hexachlorobenzene The amount of carbon tetrachloride is almost the same as the amount generated by the thermal chlorinolysis reaction alone, and carbon tetrachloride can be converted to tetrachloroethylene in a high yield. Therefore, when carrying out the above-mentioned thermal chlorinolysis reaction of hydrocarbons, the amount of carbon tetrachloride to be supplied is the amount produced by the thermal chlorinolysis reaction or more. The ratio of tetrachloroethylene and carbon tetrachloride in the composition of the product gas (reactor outlet gas) in the thermal chlorination decomposition reaction can be increased or decreased depending on the reaction conditions as is well known, and carbon tetrachloride in the product gas is supplied as carbon tetrachloride. The reaction conditions are selected such that the amount or less. By doing so, the total amount of carbon tetrachloride in the reaction product gas can be circulated to the reactor,
Carbon tetrachloride is never taken out of the system.

When the amount of carbon tetrachloride in the reaction product gas is made less than the supply amount, carbon tetrachloride separated from the reaction product gas of the thermal chlorination decomposition reaction of hydrocarbons is by-produced in another reaction. The thermal chlorination decomposition reaction of hydrocarbons may be carried out while supplementing carbon tetrachloride. Carbon tetrachloride reacts with hydrocarbons to produce tetrachloroethylene, and also reacts with hydrogen to produce tetrachloroethylene. Therefore, when converting carbon tetrachloride in an amount equal to or more than that produced by the thermal chlorinolysis reaction of hydrocarbons to tetrachloroethylene, it is possible to carry out the reaction while partially supplying hydrogen to the reaction system. The production of tetrachloroethylene in the present invention will be summarized in the following two equations when propane is shown as a typical example of the raw material. _{C 3 H 8 + 7Cl 2 →} 1.5C 2 Cl 4 + 8HCl C 3 of _{H 8 + 7CCl 4 → 5C 2} Cl 4 + 8HCl present invention method embodiment In, 11 to 25% of the required amount of chlorine gas is reacted with hydrocarbons react It is supplied in excess so that it remains in the reaction product gas in an amount of 7 to 15 mol%, preferably 8 to 12 mol%. If the chlorine concentration in the reaction product gas is lower than 7 mol%, the by-product of high boiling point substances such as hexachlorobenzene increases, and if it is higher than 15 mol%, the reaction ratio of the following formula increases the carbon tetrachloride generation ratio, which is not preferable. . C ₂ Cl ₄ + 2Cl ₂ → 2CCl ₄ The relationship between the total carbon content C (kg atom), the total hydrogen content H (kg atom), and the total chlorine content Cl (kg atom) introduced into the reactor is
When 2.5 <(Cl-H) / C <3.5, the chlorine concentration in the reaction product gas becomes 7 to 15 mol%.

The main components of the reaction product gas are hydrogen chloride, tetrachloroethylene, carbon tetrachloride, chlorine, and a small amount of high-boiling substances such as hexachlorobenzene, hexachlorobutadiene, and hexachloroethane. The total concentration of carbon tetrachloride is 5
0 mol%, preferably not more than 40 mol%. If this total concentration increases, the production of high-boiling substances increases, which is not preferable. This total concentration control is performed so that the ratio of the total carbon amount C (kg atoms) of the raw materials introduced into the reactor and the total hydrogen amount H (kg atoms) is 0.8 <H / C <1.6. Or by introducing an appropriate amount of nitrogen gas into the reactor.

The produced reaction gas is brought into contact with cold hydrochloric acid and cold water and rapidly cooled to liquefy and collect components other than chlorine. After chlorine is dehydrated, it is circulated in the reactor, and the liquefied and collected organic substances are separated by distillation. The tetrachloroethylene fraction becomes a high-purity product, tetrachloroethylene, and all the carbon tetrachloride fraction is circulated to the reactor. The carbon tetrachloride fraction may contain a small amount of tetrachloroethylene, but the amount is at most 10% or less, preferably 5% or less. If the amount of tetrachloroethylene contained in the carbon tetrachloride used in circulation is large, the by-product of high-boiling substances increases, which is not preferable.

A fraction composed of hexachloroethane and hexachlorobutadiene is pressure-chlorinated in the presence of an iron chloride catalyst to be converted into a mixture of hexachloroethane, octachlorobutene and decachlorobutane and returned to the reactor to be converted to tetrachloroethylene. be able to. Incidentally, hydrogen chloride is taken out as hydrochloric acid to be a product, and a high-boiling substance containing hexachlorobenzene as a main component is detoxified (high temperature incineration).

The present invention will be specifically described below with reference to Examples and Comparative Examples. In addition, the unit of the substance in the following examples is "parts by mass / min" unless otherwise specified.

[0015]

EXAMPLE 1 Mixture of propane 93.8, propylene chloride 250, average molecular formula C ₂ H _m Cl _n (m = 2.39, n = 2.37, the same applies hereinafter) 150, and by-product mainly consisting of hexachlorobutadiene were pressure-chlorinated. Component 61.9, chlorine 2394 and carbon tetrachloride fraction 1519 (containing 5% by weight of tetrachloroethylene, carbon tetrachloride pure content 1443) were introduced into the reactor. The pressure inside the reactor was about 105 kPa, the maximum temperature was 609 ° C, and the residence time was 2.2 seconds.
The components of the reaction product gas are hydrogen chloride 1222 and carbon tetrachloride 14
43, tetrachloroethylene 1338, chlorine 394, hexachlorobenzene 23.8, others (mainly hexachlorobutadiene, the same applies below) 47.9, the chlorine concentration in the produced gas is
It was 9.8 mol%. The produced gas was brought into contact with cold hydrochloric acid and then cold water to be rapidly cooled, and the organic component was liquefied and collected. The organic component is subjected to distillation to separate each fraction, and tetrachloroethylene
A carbon tetrachloride fraction 1519 containing 1263 and 5% by weight of tetrachloroethylene was obtained. The carbon tetrachloride fraction and chlorine were circulated to the reactor. In addition, the other component 47.9 containing hexachlorobutadiene as a main component was chlorinated under pressure and returned to the reactor (the amount after pressure chlorination was 61.9). The amount of hexachlorobenzene per 100 tetrachloroethylene products was 1.9.

[0016]

Example 2 Propane 102.5, propylene chloride 250, mixture 150 of average molecular formula C ₂ H _m Cl _n 150, component 68.4 obtained by pressure chlorinating by-product mainly consisting of hexachlorobutadiene,
Chlorine 2389, carbon tetrachloride 200, carbon tetrachloride fraction 1438 (without tetrachloroethylene) were introduced into the reactor. The pressure inside the reactor was about 105 kPa, the maximum temperature was 609 ° C., and the residence time was 2 seconds. The components of the reaction product gas were hydrogen chloride 1280, carbon tetrachloride 1438, tetrachloroethylene 1409, chlorine 389, hexachlorobenzene 29.6 and other 52.3, and the chlorine concentration in the product gas was 9.4 mol%. The produced gas was brought into contact with cold hydrochloric acid and then cold water to be rapidly cooled, and the organic component was liquefied and collected. The organic component was subjected to distillation and separated into respective fractions to obtain tetrachloroethylene 1409 and carbon tetrachloride fraction 1438. The carbon tetrachloride fraction was circulated to the reactor. Also, other component 52.3 containing hexachlorobutadiene as a main component was chlorinated under pressure and returned to the reactor (amount after pressure chlorination 68.4). The amount of hexachlorobenzene per 100 products of tetrachloroethylene was 2.1.

[0017]

[Comparative Example 1] Propane 109.3, propylene chloride 250, mixture 150 of average molecular formula C ₂ H _m Cl _n 150, component by pressure chlorination of by-product mainly consisting of hexachlorobutadiene 111.
4, chlorine 2274, and carbon tetrachloride fraction 1350 (containing 20% by weight of tetrachloroethylene) were introduced into the reactor. The pressure in the reactor was about 106 kPa, the maximum temperature was 612 ° C, and the residence time was 2 seconds.
Each component of the reaction product gas is hydrogen chloride 1325, carbon tetrachloride 10
80, tetrachloroethylene 1569, chlorine 274, hexachlorobenzene 114.9, and other 81.8, and the chlorine concentration in the produced gas was 6.7 mol%, which is lower than 7 mol%. The produced gas was brought into contact with cold hydrochloric acid and then cold water to be rapidly cooled, and the organic component was liquefied and collected. The organic component is subjected to distillation to separate each fraction,
The product tetrachlorethylene 1299 was obtained. Carbon tetrachloride fraction
1350 (containing 20% by weight of tetrachloroethylene) was circulated to the reactor. Also, other component 81.8 containing hexachlorobutadiene as a main component was chlorinated under pressure and returned to the reactor (amount 111.4 after chlorination under pressure). The amount of hexachlorobenzene per 100 products of tetrachloroethylene was 8.8.

[0018]

[Comparative Example 2] Propane 97.8, propylene chloride 250, mixture 150 of average molecular formula C ₂ H _m Cl _n , component 79.4, chlorine 2238, carbon tetrachloride 200, tetrachloromethane, which is a by-product of hexachlorobutadiene by pressure chlorination. A carbon chloride fraction 928 (containing 5% by weight of tetrachloroethylene, carbon tetrachloride pure content: 882) was introduced into the reactor. Pressure in the reactor is about 105 kPa, maximum temperature
It was 609 ° C. and the residence time was 2 seconds. The components of the reaction product gas are hydrogen chloride 1249, carbon tetrachloride 882, tetrachloroethylene 1238, chlorine 238, hexachlorobenzene 77.1, and other 59.1, and the chlorine concentration in the product gas is lower than 7 mol%.
It was 6.6 mol%. The produced gas was brought into contact with cold hydrochloric acid and then cold water to be rapidly cooled, and the organic component was liquefied and collected. The organic component is subjected to distillation to separate each fraction, and tetrachloroethylene
A carbon tetrachloride fraction 928 containing 1192 and 5% by weight of tetrachloroethylene was obtained. The carbon tetrachloride fraction was circulated to the reactor. In addition, other components containing hexachlorobutadiene as the main component
59.1 was chlorinated under pressure and returned to the reactor (the amount after chlorination under pressure was 79.4). The amount of hexachlorobenzene per 100 products of tetrachloroethylene was 6.5.

[0019]

EFFECTS OF THE INVENTION As in the present invention, while supplying carbon tetrachloride together with the starting hydrocarbons and chlorine to the system in which the thermal chlorination decomposition reaction of hydrocarbons is carried out, the chlorine gas concentration in the reaction product gas and the By adjusting the amount of carbon tetrachloride and carrying out a thermal chlorinolysis reaction and a tetrachloroethylene production reaction by carbon tetrachloride hydrocarbons, it is possible to produce tetrachloroethylene without substantially producing carbon tetrachloride. it can. Further, according to the present invention, carbon tetrachloride produced as a by-product in another production process can be converted into tetrachloroethylene, and the amount of the high-boiling substance by-product is almost different from the case where only the thermal chlorinolysis reaction is carried out. It is possible to produce tetrachlorethylene without using it.

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Claims (1)

(57) [Claims] 1. A hydrocarbon having 3 or less carbon atoms or 3 carbon atoms
While supplying the following partially chlorinated hydrocarbons or their mixtures with carbon tetrachloride, they are reacted with chlorine gas at 500 to 700 ° C to produce tetrachloroethylene, and the amount of carbon tetrachloride in the produced reaction gas is the amount of carbon tetrachloride supplied. The amount is equal to or less than the amount, and the chlorine concentration in the reaction product gas is 7 to 15
A method for producing tetrachloroethylene, characterized in that the reaction product gas is taken out in a mol% state, tetrachloroethylene is separated by distillation, and the total amount of carbon tetrachloride and chlorine gas in the reaction product gas are recycled.